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<p>The Atherton–Todd (A–T) reaction has long been regarded as a cornerstone method for synthesizing a wide array of phosphorus(V) compounds. However, despite its vast synthetic potential, achieving precise stereocontrol in this transformation remains a challenge. Here we present the highly efficient and direct asymmetric A–T reaction, using biomimetic peptide–phosphonium salt catalysts to enable the stepwise and precise synthesis of a diverse array of phosphorus(V)-based scaffolds. We demonstrate the efficient generation of three distinct stereogenic phosphorus(V) species—phosphoryl chlorides, phosphinates and phosphonates—while maintaining exceptional functional group compatibility and delivering outstanding enantioselectivity. Our mechanistic studies, complemented by density functional theory calculations, uncover the ability of the peptide–phosphonium salt catalysts to modulate the chiral environment, selectively recognizing and pre-assembling phosphorus substrates and/or nucleophilic species. This finely tuned chiral cavity facilitates a stepwise-controllable, enantioselective A–T reaction, providing an elegant strategy for the synthesis of stereochemically defined phosphorus ligands, bioactive molecules and oligonucleotides.</p><p></p>

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Stepwise-controllable catalytic asymmetric Atherton–Todd reaction to access diverse P(V)-stereogenic compounds

  • 期刊论文

  • 发表日期：

    2026年1月2日

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  • Fan Wang,
  • Jian-Ping Tan,
  • Ganlu Qian,
  • Siqiang Fang,
  • Zanjiao Liu,
  • Kehan Li,
  • Jiayan Zheng,
  • Jia-Hong Wu,
  • Xin Hong,
  • Tianli Wang

摘要

The Atherton–Todd (A–T) reaction has long been regarded as a cornerstone method for synthesizing a wide array of phosphorus(V) compounds. However, despite its vast synthetic potential, achieving precise stereocontrol in this transformation remains a challenge. Here we present the highly efficient and direct asymmetric A–T reaction, using biomimetic peptide–phosphonium salt catalysts to enable the stepwise and precise synthesis of a diverse array of phosphorus(V)-based scaffolds. We demonstrate the efficient generation of three distinct stereogenic phosphorus(V) species—phosphoryl chlorides, phosphinates and phosphonates—while maintaining exceptional functional group compatibility and delivering outstanding enantioselectivity. Our mechanistic studies, complemented by density functional theory calculations, uncover the ability of the peptide–phosphonium salt catalysts to modulate the chiral environment, selectively recognizing and pre-assembling phosphorus substrates and/or nucleophilic species. This finely tuned chiral cavity facilitates a stepwise-controllable, enantioselective A–T reaction, providing an elegant strategy for the synthesis of stereochemically defined phosphorus ligands, bioactive molecules and oligonucleotides.